JP7028530B2 - A liquid crystal alignment agent composition, a method for producing a liquid crystal alignment film using the composition, and a liquid crystal alignment film and a liquid crystal display element using the same. - Google Patents

Description

Mutual Citation with Related Application This application claims the benefit of priority based on Korean Patent Application No. 10-2018-0056586 dated May 17, 2018, and all the contents disclosed in the document of the Korean patent application. Is included as part of this specification.

Since the present invention has low discoloration even during long-term storage, it can exhibit excellent light transmittance when applied as a liquid crystal alignment film, and can realize improved orientation and electrical characteristics. The present invention relates to an object, a method for manufacturing a liquid crystal alignment film using the same, and a liquid crystal alignment film and a liquid crystal display element using the same.

In the liquid crystal display element, the liquid crystal alignment film plays a role of orienting the liquid crystal in a certain direction. Specifically, the liquid crystal alignment film acts as a director in the arrangement of the liquid crystal molecules so as to determine an appropriate direction when the liquid crystal moves by an electric field to form an image. In order to obtain uniform brightness and high contrast ratio in the liquid crystal display element, it is essential to orient the liquid crystal uniformly.

Conventionally, as one of the methods for orienting a liquid crystal display, a polymer film such as polyimide is applied to a substrate such as glass, and the surface is rubbed in a certain direction using fibers such as nylon or polyester (rubbing). The rubbing) method was used. However, in the rubbing method, when the fiber and the polymer film are rubbed against each other, fine dust and electrostatic discharge (ESD) may be generated, which may cause a serious problem in the manufacture of a liquid crystal panel.

In order to solve the problem of the rubbing method, recently, instead of rubbing, light irradiation induces anisotropy (anisotropic) in the polymer film, and the light used to arrange the liquid crystal. Anisotropy is being studied.

Various materials have been introduced as materials that can be used in the photo-alignment method, and among them, polyimide is mainly used because of the good various performances of the liquid crystal alignment film. However, polyimide has poor solvent solubility and is difficult to apply immediately in the manufacturing process of coating in a solution state to form an alignment film.

Therefore, after coating in the form of a precursor such as a polyamic acid or a polyamic acid ester having excellent solubility, a polyimide is formed through a heat treatment step at a temperature of 200 ° C. to 230 ° C., and light irradiation is performed therein. The alignment process will be performed.

However, recently, as the required performance of a liquid crystal display element has improved and a low power display is required, high electrical reliability, high light transmittance and storage stability in a high temperature environment have been emphasized.

Therefore, since the discoloration property is low even during long-term storage, the liquid crystal alignment agent composition can exhibit excellent light transmittance when applied as a liquid crystal alignment film, and can realize improved orientation and electrical characteristics. Development is required.

An object of the present invention is that since the discoloration property is low even during long-term storage, it is possible to exhibit excellent light transmittance when applied as a liquid crystal alignment film, and to realize improved orientation and electrical characteristics. The purpose is to provide an agent composition.

Another object of the present invention is to provide a method for producing a liquid crystal alignment film using the liquid crystal alignment agent composition.

Another object of the present invention is to provide a liquid crystal alignment film manufactured by the above-mentioned manufacturing method and a liquid crystal display element including the same.

［化学式２］

［化学式３］

前記化学式１から３で、Ｒ_１およびＲ_２のうちの少なくとも一つは炭素数１から１０のアルキル基であり、残りは水素であり、Ｘ_１からＸ_３は、それぞれ独立して、４価の有機基であり、Ｙ_１からＹ_３は、それぞれ独立して、下記化学式４で表される２価の有機基であり、
［化学式４］

前記化学式４で、Ａは第１５族元素であり、Ｒ_３は水素、または炭素数１から１０のアルキル基のうちの一つであり、ａは１から３の整数であり、Ｚ_１からＺ_４のうちの少なくとも一つは窒素であり、残りは炭素である。 In order to solve the above-mentioned problems, in the present specification, 1 selected from the group consisting of a repeating unit represented by the following chemical formula 1, a repeating unit represented by the following chemical formula 2, and a repeating unit represented by the following chemical formula 3. Provided is a liquid crystal alignment agent composition containing a repeat unit of a species or more, a polymer having an acid anhydride group bonded to at least one terminal; and a terminal modifier compound containing an amino group.
[Chemical formula 1]

[Chemical formula 2]

[Chemical formula 3]

In the chemical formulas 1 to 3, at least one of R ₁ and R ₂ is an alkyl group having 1 to 10 carbon atoms, the rest is hydrogen, and X ₁ to X ₃ are independently tetravalent. Y1 to Y3 _{are each} independently a divalent organic group represented by the following chemical formula 4.
[Chemical formula 4]

In the chemical formula 4, A is a Group 15 element, R ₃ is hydrogen, or one of the alkyl groups having 1 to 10 carbon atoms, a is an integer of 1 to 3, and Z ₁ to Z. At least one of the _four is nitrogen and the rest is carbon.

Also in the present specification, the step of applying the liquid crystal alignment agent composition to a substrate to form a coating film; the step of drying the coating film; the step of irradiating the dried coating film with light or rubbing the dried coating film. Provided is a method for producing a liquid crystal alignment film, which comprises a step of aligning and curing; and a step of heat-treating and curing the oriented coating film.

The present specification also provides a liquid crystal alignment film manufactured by a method for manufacturing a liquid crystal alignment film and a liquid crystal display element including the same.

Hereinafter, a liquid crystal alignment agent composition according to a specific embodiment of the invention, a method for producing a liquid crystal alignment film using the same, and a liquid crystal alignment film using the same will be described in more detail.

I. Liquid crystal aligning agent composition According to one embodiment of the invention, it was selected from the group consisting of the repeating unit represented by the chemical formula 1, the repeating unit represented by the chemical formula 2, and the repeating unit represented by the chemical formula 3. A liquid crystal alignment agent composition containing one or more repeating units, a polymer having an acid anhydride group bonded to at least one terminal; and a terminal modifier compound containing an amino group can be provided.

The present inventors mainly use one or more repeating units selected from the group consisting of a polyamic acid repeating unit, a polyamic acid ester repeating unit, and a polyimide repeating unit, as in the liquid crystal alignment agent composition of the above embodiment. It is present at the end of the main chain of the polymer by adding a terminal modifier compound containing an amino group to the polymer contained as a chain and having an acid anhydride group bonded to at least one end of the main chain. Even if the acid anhydride group reacts with the amino group of the terminal modifier compound to modify the acid anhydride group, which is the reactive acting group at the end of the main chain, into an imide group, an amic acid group, or an amic acid ester group. Well, this allows the liquid crystal alignment film obtained from the liquid crystal alignment agent composition to have a higher light transmittance than before the addition of the terminal modifier compound, and in the liquid crystal cell on which the liquid crystal alignment film is installed. The invention was completed after confirming through experiments that improved electrical reliability and orientation characteristics could be achieved.

Specifically, the acid anhydride group at the end of the main chain of the polymer is modified into an imide group, an amic acid group, an amic acid ester group, or the like by the terminal modifier compound contained in the liquid crystal alignment agent composition. As a result, it is possible to prevent the oxidation of the acid anhydride group and have a high light transmittance in the liquid crystal alignment film, and realize further improved electrical reliability and orientation characteristics in the liquid crystal cell in which the liquid crystal alignment film is installed. can do.

In particular, in the present invention, a polymer for a liquid crystal alignment agent containing a repeating unit of the above chemical formula 4 produced from a reaction product containing a diamine compound having a specific structure containing a nitrogen atom is used to obtain a high initial voltage retention rate at a high temperature. The invention was completed after confirming that it was possible to realize excellent electrical characteristics such as a small change in the voltage retention rate during long-term storage, a decrease in the contrast ratio, and an improvement in afterimage development. Hereinafter, the present invention will be described in more detail.

Unless otherwise specified herein, the following terms are defined as follows:

As used herein, when a component is referred to as "contains" a component, it is possible to include other components as well, rather than excluding other components, unless otherwise stated. means.

Examples of substituents are described herein below, but are not limited thereto.

As used herein, the term "substitution" means that another working group is attached instead of a hydrogen atom in the compound, where the substituted position is the position where the hydrogen atom is substituted, that is, the substituent is. The position is not limited as long as it can be substituted, and when two or more substituents are substituted, the two or more substituents may be the same or different from each other.

As used herein, the term "substituted or unsubstituted" refers to a heavy hydrogen; a halogen group; a cyano group; a nitro group; a hydroxy group; a carbonyl group; an ester group; an imide group; an amide group; a primary amino group; a carboxy group. Group; Sulfonic acid group; Sulfonamide group; Phosphine oxide group; alkoxy group; Aryloxy group; Alkylthioxy group; Arylthioxy group; Alkylsulfoxy group; Alkyl group; alkenyl group; aryl group; alalkyl group; alalkenyl group; alkylaryl group; alkoxysilylalkyl group; arylphosphin group; or a heterocyclic group containing one or more of N, O and S atoms. It means that it has been substituted or unsubstituted with one or more substituents selected from the group, or that two or more of the above exemplified substituents have been linked and substituted. For example, the "substituent in which two or more substituents are linked" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which two phenyl groups are linked.

は、他の置換基に連結される結合を意味し、直接結合はＬで表される部分に別途の原子が存在しないことを意味する。 In this specification,

Means a bond linked to another substituent, and a direct bond means that there is no separate atom in the portion represented by L.

In the present specification, the alkyl group is a monovalent acting group derived from an alkane, and may be a straight chain or a branched chain, and the number of carbon atoms of the straight chain alkyl group is not particularly limited. It is preferably 1 to 20. Further, the number of carbon atoms of the branched-chain alkyl group is 3 to 20. Specific examples of alkyl groups include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, Pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , N-Heptyl, 1-methylhexyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl , 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, 2,6-dimethylheptane-4-yl and the like, but are not limited thereto. The alkyl group may be substituted or unsubstituted.

In the present specification, the cycloalkyl group is a monovalent acting group derived from cycloalkane, and may be monocyclic or polycyclic, and is not particularly limited, but has 3 to 20 carbon atoms. Is. Further, according to one embodiment, the cycloalkyl group has 3 to 10 carbon atoms. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, There are, but are not limited to, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, bicyclo [2,2,1] heptyl and the like. The cycloalkyl group may be substituted or unsubstituted.

In the present specification, the aryl group is a monovalent agonist derived from arene, and is not particularly limited, but preferably has 6 to 20 carbon atoms, and is a monocyclic aryl group or a polycyclic aryl group. It may be a group. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group or the like as the monocyclic aryl group, but is not limited thereto. The polycyclic aryl group can be, but is not limited to, a naphthyl group, an anthrasenyl group, a phenanthryl group, a pyrenyl group, a peryleneyl group, a chrysenyl group, a fluorenyl group and the like. The aryl group may be substituted or unsubstituted.

In the present specification, the heteroaryl group contains one or more non-carbon atoms and heteroatoms, and specifically, the heteroatom is one atom selected from the group consisting of O, N, Se, S and the like. The above can be included. The number of carbon atoms is not particularly limited, but is preferably 4 to 20, and the heteroaryl group may be monocyclic or polycyclic. Examples of heterocyclic groups include thiophene group, furanyl group, pyrrole group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, triazinyl group, triazolyl group, acrizyl group and pyridadinyl group. Pyrazineyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidyl group, pyridopyrazinyl group, pyrazinopyrazinyl group, isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzoimidazolyl group, benzothiazolyl group, benzo Carbazolyl group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthrolinyl group, thiazolyl group, isooxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, azylidyl group, azaindrill group, Isoindryl group, indazolyl group, purine group, pteridinyl group, β-carbonyl group, naphthylidyl group, terpyridyl group, phenazinyl group, imidazole pyridyl group, pyropyridyl group, azepine group, pyrazolyl group and dibe There are, but are not limited to, nzofuranyl groups. The heteroaryl group may be substituted or unsubstituted.

As used herein, the haloalkyl group means an acting group in which a halogen group is substituted with the above-mentioned alkyl group, and examples of the halogen group include fluorine, chlorine, bromine and iodine. The haloalkyl group may be substituted or unsubstituted.

In the present specification, the alkylene group is a divalent working group derived from an alkane, and the above-mentioned description of the alkyl group is applicable except that these are divalent working groups. .. For example, it may be a linear type or a branched type, and may be a methylene group, an ethylene group, a propylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, a pentylene group, a hexylene group or the like. The alkylene group may be substituted or unsubstituted.

In the present specification, the haloalkylene group is an active group in which one or more hydrogen atoms contained in a divalent active group derived from an alkane are substituted with a halogen. Examples of halogen groups are fluorine, chlorine, bromine or iodine.

In the present specification, the cycloalkylene group is a divalent working group derived from a cycloalkane, and the above-mentioned description of the cycloalkyl group is applicable except that these are divalent working groups. .. The cycloalkylene group may be substituted or unsubstituted.

As used herein, the heterocycloalkylene group has 3 to 20, or 3 to 10, or 6 to 20 carbon atoms. The above-mentioned description of the cycloalkylene group is applicable except that it is a cycloalkylene group containing O, N or S as a hetero atom and is a divalent acting group. The heterocycloalkylene group may be substituted or unsubstituted.

In the present specification, the arylene group is a divalent acting group derived from arene, and the above-mentioned description of the aryl group is applicable except that these are divalent acting groups. For example, it may be a linear type or a branched type, and may be a phenylene group, a biphenylene group, a terphenylene group, or the like. The arylene group may be substituted or unsubstituted.

As used herein, the heteroarylene group has 2 to 20, or 2 to 10, or 6 to 20 carbon atoms. The above-mentioned description of the heteroaryl group is applicable except that it is an arylene group containing O, N or S as a hetero atom and is a divalent acting group. The heteroarylene group may be substituted or unsubstituted.

In the present specification, the fluoroalkyl group having 1 to 10 carbon atoms may be one in which one or more hydrogens of the alkyl group having 1 to 10 carbon atoms are substituted with hydrogen, and the fluoroalkyl group has 1 to 10 carbon atoms. The fluoroalkoxy group may be one in which one or more hydrogens of the alkoxy group having 1 to 10 carbon atoms are substituted with fluorine.

As used herein, the halogen may be fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

As used herein, the Group 15 element may be nitrogen (N), phosphorus (P), arsenic (As), antimony (Sb) or bismuth (Bi).

In the present specification, the nitrogen oxide is a compound in which a nitrogen atom and an oxygen atom are bonded, and the nitrogen oxide working group means a working group containing a nitrogen oxide in the working group. To give an example of the nitrogen oxide acting group, a nitro group (-NO ₂ ) or the like can be used.

In the present specification, a multivalent organic group is a residue in which a plurality of hydrogen atoms bonded to an arbitrary compound have been removed, and is, for example, a divalent organic group, a trivalent organic group, or a tetravalent group. Organic groups can be mentioned. As an example, a tetravalent organic group derived from cyclobutane means a residue in the form in which any four hydrogen atoms attached to cyclobutane have been removed.

As used herein, a direct bond or a single bond means that any atom or group of atoms is not present at that position and is therefore connected by a bond line. Specifically, it means that there is no separate atom in the portion represented by L ₁ and L ₂ in the chemical formula.

(1) Polymer The polymer is one or more selected from the group consisting of the repeating unit represented by the chemical formula 1, the repeating unit represented by the chemical formula 2, and the repeating unit represented by the chemical formula 3. It can include one or more selected from the group consisting of repeating units.

That is, the polymer has one repeating unit represented by the chemical formula 1, one repeating unit represented by the chemical formula 2, one repeating unit represented by the chemical formula 3, or two or more repeating units thereof. It can include a mixed copolymer.

The repeating unit represented by the chemical formula 1 corresponds to a polyimide repeating unit, the repeating unit represented by the chemical formula 2 corresponds to a polyamic acid ester repeating unit, and the repeating unit represented by the chemical formula 3 corresponds to a polyamic acid repeating unit. In this polymer, one polyamic acid repeating unit, one polyamic acid ester repeating unit, one polyimide repeating unit, or two or more of these repeating units are mixed or bonded together. It can contain polymers.

One or more repeating units selected from the group consisting of the repeating unit represented by the chemical formula 1, the repeating unit represented by the chemical formula 2 and the repeating unit represented by the chemical formula 3 is the main chain of the polymer. Can form

In the repeating units of the chemical formulas 1 to 3, X ₁ to X ₃ may be the same or different from each other and may be independently tetravalent organic groups. _The X1 to X3 may be a polyamic acid _, a polyamic acid ester, or an active group derived from a tetracarboxylic acid anhydride compound used at the time of polyimide synthesis.

前記化学式５で、Ｒ_４からＲ_９は、それぞれ独立して、水素、または炭素数１から１０のアルキル基であり、Ｌ_１は直接結合、－Ｏ－、－ＣＯ－、－Ｓ－、－ＳＯ－、－ＳＯ_２－、－ＣＲ_１０Ｒ_１１－、－ＣＯＮＨ－、－ＣＯＯ－、－（ＣＨ_２）_ｂ－、－Ｏ（ＣＨ_２）_ｂＯ－、－ＣＯＯ－（ＣＨ_２）_ｂ－ＯＣＯ－、フェニレンまたはこれらの組み合わせからなる群より選択されたいずれか一つであり、Ｒ_１０およびＲ_１１は、それぞれ独立して、水素、炭素数１から１０のアルキル基、または炭素数１から１０のハロアルキル基であり、ｂは１から１０の整数である。 More specifically, the X ₁ to X ₃ may be independently one of the tetravalent organic groups represented by the following chemical formula 5.
[Chemical formula 5]

In the chemical formula 5, R ₄ to R ₉ are independently hydrogen or an alkyl group having 1 to 10 carbon atoms, and L ₁ is a direct bond, -O-, -CO-, -S-,-. SO-, -SO _2- , -CR ₁₀ R _11- , -CONH-, -COO-,-(CH ₂ ) _b- , -O (CH ₂ ) _b O-, -COO- (CH ₂ ) _b- One selected from the group consisting of OCO-, phenylene or a combination thereof, R ₁₀ and R ₁₁ are independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms, respectively. It is a haloalkyl group of 10 and b is an integer from 1 to 10.

［化学式５－２］

［化学式５－３］

［化学式５－４］

Specifically, X ₁ to X ₃ are independently organic groups of the following chemical formula 5-1 derived from pyromylic acid dianhydride (PMDA); 3,3', 4,4'-. Organic group of the following chemical formula 5-2 derived from biphenyltetracarboxylic acid dianhydride (3,3', 4,4'-Biphenyl Terracarboxyl Acid Dianhydride, BPDA); 1,2,4,5-cyclohexanetetracarboxylic acid di. Organic group of the following chemical formula 5-3 derived from anhydrate (1,2,4,5-Cyclohexanetracarboxylic Dianhydride, HPMDA); or 1,3-dimethyl-cyclobutane-1,2,3,4-tetracarboxylic acid dianhydride. It may be an organic group of the following chemical formula 5-4 derived from a substance (DMCBDA).
[Chemical formula 5-1]

[Chemical formula 5-2]

[Chemical formula 5-3]

[Chemical formula 5-4]

More preferably, the organic group of the chemical formula 5-2 derived from 3,3', 4,4'-biphenyltetracarboxylic dianhydride can be used.

On the other hand, in the chemical formulas 1 to 3, Y ₁ to Y ₃ may be the same or different from each other, and may be independently divalent organic groups. _The Y1 to Y3 may be a polyamic acid _, a polyamic acid ester, or a working group derived from a diamine compound used in the synthesis of polyimide.

As a specific example, the Y ₁ to Y ₃ may be a divalent organic group represented by the chemical formula 4.

In the chemical formula 4, A is a Group 15 element, R ₃ is hydrogen, or an alkyl group having 1 to 10 carbon atoms, a is an integer of 1 to 3, and at least Z ₁ to Z ₄ are present. One, that is, one or more is nitrogen and the rest is carbon.

The Group 15 element may be nitrogen (N), phosphorus (P), arsenic (As), antimony (Sb) or bismuth (Bi). The R ₃ can be bonded to the element A as the number of the number represented by a as the acting group to be bonded to the A. Preferably, in the chemical formula 4, A may be nitrogen, R ₃ may be hydrogen, and a may be 1.

On the other hand, in the chemical formula 4, at least one of Z ₁ to Z ₄ is nitrogen, and the rest satisfies carbon, so that the chemical formula 4 is symmetrical with respect to the center point or the center line due to the nitrogen atom. It is possible to form an asymmetrical structure that does not become. The chemical formula 4 is an active group derived from a diamine, which is a precursor used for forming a polymer for a liquid crystal alignment agent, and is considered to be due to the use of an asymmetric diamine as described later.

The working group of the above chemical formula 4 and its precursor diamine in that the composition for the asymmetric diamine or the repeating unit derived from the asymmetric diamine and the effect thereof are not recognized at all in the existing known polymer field for liquid crystal alignment agents. The compound appears to be novel.

More specifically, in the above chemical formula 4, one of Z ₁ to Z ₄ may be nitrogen and the rest may be carbon, and in the above chemical formula 4, one of Z ₁ or Z ₃ is nitrogen. Yes, the rest is carbon, and Z ₂ and Z ₄ may be carbon. That is, the aromatic ring containing Z ₁ to Z ₄ in the chemical formula 4 can have a pyridine structure. As a result, the liquid crystal display element to which the polymer for liquid crystal alignment agent of the above embodiment is applied can realize a high voltage retention rate and liquid crystal orientation.

On the other hand, when the two aromatic ring compounds are bonded in a single bond without a secondary amine group or a tertiary amine group, the brightness fluctuation rate of the liquid crystal alignment agent increases, the afterimage characteristics are poor, and the voltage Technical problems may occur in which the retention rate is significantly reduced.

Further, when each of the two aromatic ring compounds bonded through the secondary amine group or the tertiary amine group does not contain a nitrogen atom, the polyamic acid or polyamic acid ester formed by the reaction of the amine and the acid anhydride is formed. However, even if the imidization reaction proceeds, there is a limit that the imidization rate decreases in the final liquid crystal alignment film because the imidization reaction cannot proceed sufficiently (for example, through 230 ° C. heat treatment).

Further, the active group represented by the chemical formula 4 has only an amine group and hydrogen bonded to each of the two aromatic ring compounds, preferably the heteroaromatic ring compound and the aromatic ring compound, respectively. It is characterized in that no other substituent is introduced, and when a substituent such as a fluoroalkyl group is introduced into the heteroaromatic ring compound or the aromatic ring compound, the brightness fluctuation rate increases and the afterimage characteristics are poor. Technical problems may occur in which the voltage retention is significantly reduced.

［化学式４－２］

［化学式４－３］

Further, the chemical formula 4 can contain one or more active groups selected from the group consisting of the following chemical formulas 4-1 and 4-2 and 4-3.
[Chemical formula 4-1]

[Chemical formula 4-2]

[Chemical formula 4-3]

The contents of A, R3 _{, a} , Z1, Z2, Z3 _, and Z4 described in Chemical Formula 4-1 and Chemical Formula _4-2 and Chemical Formula 4-3 include the contents described above in Chemical Formula ₄ . ..

As described above, the working group of the chemical formula 4 contains one or more working groups selected from the group consisting of the chemical formula 4-1 and the chemical formula 4-2 and the chemical formula 4-3, thereby achieving more excellent liquid crystal orientation. It can be realized.

［化学式４－５］

［化学式４－６］

More preferably, in the chemical formulas 4-1 to 4-3, A is nitrogen, R ₃ is hydrogen, a is 1, one of Z ₁ or Z ₃ is nitrogen, and the rest. It is carbon, and Z ₂ and Z ₄ may be carbon. Specifically, the chemical formula 4 can contain one or more working groups selected from the group consisting of the following chemical formulas 4-4, 4-5 and 4-6.
[Chemical formula 4-4]

[Chemical formula 4-5]

[Chemical formula 4-6]

That is, in the above chemical formula 4-1 A is nitrogen, R ₃ is hydrogen, a is 1, one of Z ₁ or Z ₃ is nitrogen, and the rest is carbon, Z ₂ And Z ₄ are the working groups represented by the above chemical formula 4-4 when they are carbon. Further, in the above chemical formula 4-2, A is nitrogen, R ₃ is hydrogen, a is 1, one of Z ₁ or Z ₃ is nitrogen, and the rest is carbon, Z ₂ And Z ₄ are the working groups represented by the above chemical formula 4-5 when they are carbon. Further, in the above chemical formula 4-3, A is nitrogen, R ₃ is hydrogen, a is 1, one of Z ₁ or Z ₃ is nitrogen, and the rest is carbon, Z ₂ And Z ₄ are the working groups represented by the above chemical formula 4-6 when they are carbon.

On the other hand, the polymer can have an acid anhydride group bonded to at least one end. That is, the polymer contains a repeating unit represented by the above-mentioned chemical formulas 1 to 3 as a main chain, and an acid anhydride group (anhydride group) is bonded to any one or more of both ends of the main chain. Can exist in the same state.

Examples of the method of attaching an acid anhydride group to at least one end of the polymer are not largely limited, and for example, a diamine compound and tetracarboxylic acid anhydride which are reaction monomers used in the production of the polymer are not limited. Among the compound compounds, a method of adding the molar content of the tetracarboxylic acid anhydride compound in an excess amount of the molar content of the diamine compound can be used.

［化学式８］

［化学式９］

前記化学式７から９で、Ｒ_１'およびＲ_２'のうちの少なくとも一つは炭素数１から１０のアルキル基であり、残りは水素であり、Ｘ_１'からＸ_３'は、それぞれ独立して、４価の有機基であり、Ｙ_１'からＹ_３'は、それぞれ独立して、下記化学式４で表される２価の有機基であり、Ｌ_２'およびＬ_３'は、それぞれ独立して、直接結合、－Ｏ－、－ＣＯ－、－Ｓ－、－ＣＯＮＨ－、－ＣＯＯ－、－Ｏ（ＣＨ_２）_ｔＯ－、－ＣＯＯ－（ＣＨ_２）_ｔ－ＯＣＯ－、炭素数１から１０のアルキレン基、炭素数１から１０のハロアルキレン基、炭素数３から２０のシクロアルキレン基、炭素数３から２０のヘテロシクロアルキレン基、炭素数６から３０のアリーレン基、または炭素数３から２０のヘテロアリーレン基のうちの一つであり、ｔは１から１０の整数であり、Ｘ'は水素、ヒドロキシ基、ニトロ基、または炭素数１から１０のアルキル基のうちの一つであり、
［化学式４］

前記化学式４で、Ａは第１５族元素であり、Ｒ_３は水素、または炭素数１から１０のアルキル基のうちの一つであり、ａは１から３の整数であり、Ｚ_１からＺ_４のうちの少なくとも一つは窒素であり、残りは炭素である。 On the other hand, the polymer contains one or more repeating units selected from the group consisting of the repeating unit represented by the chemical formula 1, the repeating unit represented by the chemical formula 2, and the repeating unit represented by the chemical formula 3. When a polymer having an acid anhydride group bonded to at least one terminal is referred to as a first polymer, in addition to the first polymer, a repeating unit represented by the chemical formula 1, a repeating unit represented by the chemical formula 2, and a chemical formula 3 are used. It contains one or more repeating units selected from the group consisting of the repeating units represented by, and has at least one terminal action group selected from the group consisting of the following chemical formulas 7, 8 and 9 at least at one end. The containing second polymer can be further contained.
[Chemical formula 7]

[Chemical formula 8]

[Chemical formula 9]

In the chemical formulas 7 to 9, at least _one of R 1'and R _2'is an alkyl group having 1 to 10 carbon atoms, the rest is hydrogen, and X _1'to X _3'are independent of each other. Y _1'to Y _3'are independent divalent organic groups represented by the following chemical formula 4, and L _2'and L _3'are independent of each other. Then, direct bond, -O-, -CO-, -S-, -CONH-, -COO-, -O (CH ₂ ) _t O-, -COO- (CH ₂ ) _t -OCO-, carbon number 1 to 10 alkylene groups, 1 to 10 carbon haloalkylene groups, 3 to 20 carbon cycloalkylene groups, 3 to 20 carbon heterocycloalkylene groups, 6 to 30 carbon arylene groups, or carbons One of 3 to 20 heteroarylene groups, t is an integer of 1 to 10, X'is one of hydrogen, hydroxy group, nitro group, or alkyl group with 1 to 10 carbon atoms. And
[Chemical formula 4]

In the chemical formula 4, A is a Group 15 element, R ₃ is hydrogen, or one of the alkyl groups having 1 to 10 carbon atoms, a is an integer of 1 to 3, and Z ₁ to Z. At least one of the _four is nitrogen and the rest is carbon.

Specifically, the second polymer is a repeating unit represented by the chemical formula 1, a repeating unit represented by the chemical formula 2, and the chemical formula 3 contained in the liquid crystal aligning agent composition of the above embodiment. The amino group-containing terminal modifier compound reacts with a polymer containing one or more selected from the group consisting of the represented repeating units and having an acid anhydride group bonded to at least one terminal. , Corresponds to the reaction result obtained by modifying the terminal acid anhydride group.

That is, the acid anhydride group bonded to at least one terminal of the polymer may react with the terminal modifier compound to be modified to an imide group, an amic acid group, or an amic acid ester group.

In the chemical formulas 7 to 9, X _1'to X _3'may be the same or different from each other and may be independently tetravalent organic groups. The X _1'to X _3'may be an active group derived from a polyamic acid, a polyamic acid ester, or a tetracarboxylic acid anhydride compound used at the time of polyimide synthesis.

More specifically, the X 1'to X _3'may be independently _one of the tetravalent organic groups represented by the chemical formula 5.

Further, in the chemical formulas 7 to 9, Y _1'to Y _3'may be the same or different from each other, and may be independently divalent organic groups. The Y _1'to Y _3'may be an active group derived from a polyamic acid, a polyamic acid ester, or a diamine compound used in the synthesis of polyimide. As a specific example, the Y _1'to Y _3'may be a divalent organic group represented by the chemical formula 4.

Further, in the chemical formulas 7 to 9, at least _one of R 1'and R _2'may be an alkyl having 1 to 10 carbon atoms, and the rest may be hydrogen.

The second polymer is 0.5% by weight to 40% by weight, or 1% by weight to 30% by weight, or 1% by weight to 20% by weight, or 1% by weight to 10% by weight based on the entire liquid crystal alignment agent composition. It may be contained in% by weight. That is, the liquid crystal alignment agent composition includes a first polymer in which an acid anhydride group is bonded to at least one terminal, a terminal modifier, and a second polymer in which the acid anhydride group is modified by the terminal modifier. May be mixed.

When the second polymer is excessively reduced to less than 0.5% by weight with respect to the entire liquid crystal alignment agent composition, the degree of modification of the polymer terminal is slight, and the light transmittance of the liquid crystal alignment agent composition, It is difficult to sufficiently improve the electrical characteristics. Further, when the second polymer is excessively increased by more than 40% by weight with respect to the entire liquid crystal alignment agent composition, there is a limit that the orientation property and the electrical property peculiar to the polymer are deteriorated.

(2) Terminal modifier compound containing an amino group The liquid crystal alignment agent composition of the above embodiment may contain an amino group-containing terminal modifier compound in addition to the above-mentioned polymer, and the terminal may be contained. The above-mentioned polymer terminal acid anhydride group can be effectively modified by the amino group contained in the modifier compound. Therefore, when a terminal modifier containing an action group that is chemically difficult to react with the acid anhydride group at the polymer terminal is used, it is difficult to obtain the level of effect realized by the present invention.

As the terminal modifier compound containing an amino group, various organic compounds or inorganic compounds containing an amino group in the molecule can be used, and the types of the organic compound or the inorganic compound are largely limited. is not it.

Preferably, a monoamine compound containing one amino group can be used as the terminal modifier compound. When a polyvalent amine containing two or more amino groups is used as the terminal modifier compound, the monomer of the polymer (for example, tetra) is used after the modification reaction with the acid anhydride group at the terminal of the polymer. As the side reaction with (carboxylic acid anhydride) or the like proceeds, the viscosity of the liquid crystal alignment agent composition increases, which may cause a problem caused by a printing error.

前記化学式６で、Ｌ_２およびＬ_３は、それぞれ独立して、直接結合、－Ｏ－、－ＣＯ－、－Ｓ－、－ＣＯＮＨ－、－ＣＯＯ－、－Ｏ（ＣＨ_２）_ｔＯ－、－ＣＯＯ－（ＣＨ_２）_ｔ－ＯＣＯ－、炭素数１から１０のアルキレン基、炭素数１から１０のハロアルキレン基、炭素数３から２０のシクロアルキレン基、炭素数３から２０のヘテロシクロアルキレン基、炭素数６から３０のアリーレン基、または炭素数３から２０のヘテロアリーレン基のうちの一つであり、ｔは１から１０の整数であり、Ｘは水素、ヒドロキシ基、ニトロ基、または炭素数１から１０のアルキル基のうちの一つである。 Specific examples of the terminal modifier compound containing an amino group include a compound represented by the following chemical formula 6.
[Chemical formula 6]

In the above chemical formula 6, L ₂ and L ₃ are independently bonded, directly bonded, -O-, -CO-, -S-, -CONH-, -COO-, -O (CH ₂ ) _t O-, respectively. -COO- (CH ₂ ) _t -OCO-, alkylene group having 1 to 10 carbon atoms, haloalkylene group having 1 to 10 carbon atoms, cycloalkylene group having 3 to 20 carbon atoms, heterocycloalkylene group having 3 to 20 carbon atoms. A group, one of an arylene group having 6 to 30 carbon atoms, or a heteroarylene group having 3 to 20 carbon atoms, where t is an integer of 1 to 10 and X is a hydrogen, hydroxy group, nitro group, or It is one of the alkyl groups having 1 to 10 carbon atoms.

More preferably, the terminal modifier compound represented by the chemical formula 6 may be 1,3-aminophenol in which L ₂ is a direct bond, L ₃ is a phenylene group having 6 carbon atoms, and X is a hydroxy group. good. Further, the terminal modifier compound represented by the chemical formula 6 may be an aniline in which L ₂ is a direct bond, L ₃ is a phenylene group having 6 carbon atoms, and X is hydrogen.

The amino group-containing terminal modifier compound is 0.1% by weight to 20% by weight, or 1% by weight to 20% by weight, or 1% by weight to 10% by weight based on the total weight of the liquid crystal alignment agent composition. It may be contained in%, or 1% by weight to 5% by weight. If the content of the terminal modifier compound is excessively high, there is a limit that the number of repeating units of the molecule is reduced and the orientation property and the electrical property peculiar to the polymer are deteriorated.

On the other hand, if the content of the terminal modifier compound becomes excessively small, the effect of improving the light transmittance and the electrical characteristics by modifying the terminal acid anhydride group of the polymer for liquid crystal alignment agent is sufficiently realized. It can be difficult.

II. Method for producing a liquid crystal alignment film Further, the present invention is a step of applying the liquid crystal alignment agent composition of the above embodiment to a substrate to form a coating film (step 1); a step of drying the coating film (step 2). The dried coating film is subjected to light irradiation or rubbing treatment to be oriented (step 3); and the oriented coating film is heat-treated and cured (step 4). A method for producing a liquid crystal alignment film is provided.

The step 1 is a step of applying the liquid crystal alignment agent composition described above to a substrate to form a coating film. The content relating to the liquid crystal alignment agent composition includes all the contents described above in the above embodiment.

The method of applying the liquid crystal alignment agent composition to the substrate is not particularly limited, and for example, screen printing, offset printing, flexographic printing, inkjet printing, or the like may be used.

The liquid crystal alignment agent composition may be dissolved or dispersed in an organic solvent. Specific examples of the organic solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactum, 2-pyrrolidone, N-ethylpyrrolidone and N-vinyl. Pyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropaneamide, 3-butoxy- N, N-dimethylpropanamide, 1,3-dimethyl-imidazolidinone, ethylamyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglime, 4-hydroxy- 4-Methyl-2-pentanone, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monopropyl ether acetate, ethylene glycol monoisopropyl ether , Ethylene glycol monoisopropyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate and the like. These may be used alone or in combination.

Further, the liquid crystal alignment agent composition may additionally contain other components in addition to the organic solvent. As a non-limiting example, when the liquid crystal alignment agent composition is applied, the uniformity of the film thickness and the surface smoothness are improved, or the adhesion between the liquid crystal alignment film and the substrate is improved, or Additives that can change the dielectric constant and conductivity of the liquid crystal alignment film or increase the density of the liquid crystal alignment film may be additionally contained. Examples of such additives include various solvents, surfactants, silane compounds, dielectrics, crosslinkable compounds and the like.

The step 2 is a step of applying the liquid crystal alignment agent composition to the substrate and drying the formed coating film.

The drying step of the coating film may be carried out by a heating means such as a hot plate, a hot air circulation furnace, an infrared furnace, etc., and may be carried out at a temperature of 50 ° C to 150 ° C, or 50 ° C to 100 ° C.

The step 3 is a step of irradiating the dried coating film with light or performing a rubbing treatment to perform an orientation treatment.

The light irradiation at the step of the alignment treatment may be to irradiate polarized ultraviolet rays having a wavelength of 150 nm to 450 nm. At this time, the intensity of exposure varies depending on the type of the polymer for the liquid crystal alignment agent, and energy of 10 mJ / cm ² to 10 J / cm ² , preferably 30 mJ / cm ² to 2 J / cm ² can be irradiated. ..

The ultraviolet rays include a polarizing device using a transparent substrate surface coated with a dielectric anisotropic substance such as quartz glass, sodalime glass, and sodalime-free glass, and polarization with finely vapor-deposited aluminum or metal wire. Alignment processing is performed by irradiating polarized ultraviolet rays selected from ultraviolet rays that have been polarized by a method that passes through or is reflected by a plate or a blue star polarizing device that reflects quartz glass. At this time, the polarized ultraviolet rays can be irradiated vertically to the substrate surface, or can be irradiated to a specific angle with an incident angle inclined. By such a method, the orientation ability of the liquid crystal molecules is imparted to the coating film.

Further, in the rubbing treatment at the stage of the orientation treatment, a method using a rubbing cloth can be used. More specifically, in the rubbing treatment, the surface of the coating film after the heat treatment step can be rubbed in one direction while rotating the rubbing roller in which the woven fabric of the rubbing cloth is attached to the metal roller.

The step 4 is a step of heat-treating and curing the oriented coating film. At this time, the heat treatment may be carried out by a heating means such as a hot plate, a hot air circulation furnace, an infrared furnace, etc., and may be carried out at a temperature of 180 ° C to 300 ° C or 200 ° C to 300 ° C.

III. Liquid crystal alignment film The present invention also provides a liquid crystal alignment film manufactured by the method for producing a liquid crystal alignment film described above. Specifically, the liquid crystal alignment film can contain an alignment cured product of the liquid crystal alignment agent composition of the above embodiment. The oriented cured product means a substance obtained through the alignment step and the curing step of the liquid crystal alignment agent composition of the above embodiment.

As described above, the present invention comprises one or more repeating units selected from the group consisting of the repeating unit represented by the chemical formula 1, the repeating unit represented by the chemical formula 2, and the repeating unit represented by the chemical formula 3. When a liquid crystal alignment agent composition containing a polymer having an acid anhydride group bonded to at least one terminal; and a terminal modifier compound containing an amino group is used, it has a high light transmittance and excellent orientation and excellent orientation. A liquid crystal alignment film having electrical properties can be produced.

The thickness of the liquid crystal alignment film is not largely limited, but can be freely adjusted, for example, within the range of 0.001 μm to 100 μm. When the thickness of the liquid crystal alignment film increases or decreases by a specific numerical value, the physical properties measured by the alignment film can also change by a certain numerical value.

Specifically, in the liquid crystal alignment film, the amount of change in permeability measured by the following formula 2 is 0.75% or less, 0.7% or less, or 0.1% to 0.75%, or 0.2. It may be% to 0.75%, or 0.3% to 0.7%. The amount of change in viscosity of the liquid crystal alignment film may be, for example, a value measured for a liquid crystal alignment film having a thickness of 0.01 μm to 10 μm or 0.05 μm to 50 μm.
[Formula 2]
Transmittance rate of change (%) = 2nd liquid crystal alignment film transmittance-1st liquid crystal alignment film transmittance

The specific method for measuring the transmittance in the above formula 2 is not largely limited, but for example, the transmittance is measured at a wavelength of 400 nm using the JASCO Asia Portal V-770 UV-VIS-NIR Spectrophotometer equipment. Can be used.

Further, in the liquid crystal alignment film, the amount of change in viscosity measured by the following formula 3 is 10 cps or less, 5 cps or less, or 3 cps or less, or 0.1 cps to 10 cps, or 0.1 cps to 5 cps, or 0.1 cps to 3 cps. , Or may be from 2.01 cps to 2.41 cps. The amount of change in viscosity of the liquid crystal alignment film may be, for example, a value measured for a liquid crystal alignment film having a thickness of 0.01 μm to 10 μm or 0.05 μm to 50 μm.
[Formula 3]
Viscosity change amount (cps) = (Viscosity of liquid crystal alignment film after storage at room temperature for 30 days-viscosity of first liquid crystal alignment film)

Examples of specific methods for measuring viscosity according to the above formula 3 are not largely limited, but for example, a temperature of 25 ° C., a rotation speed of 0.5 rpm, and rotation with a Brookfield viscometer on an RV-7 spindle. A method of measuring by force (torque) can be used.

IV. Liquid crystal display element The present invention also provides a liquid crystal display element including the above-mentioned liquid crystal alignment film.

The liquid crystal alignment film may be introduced into a liquid crystal cell by a known method, and the liquid crystal cell may be similarly introduced into a liquid crystal display element by a known method. The liquid crystal alignment film is produced from the liquid crystal alignment agent composition of the above embodiment and can realize excellent stability as well as excellent various physical characteristics. This makes it possible to provide a liquid crystal display element capable of showing high reliability.

On the other hand, the liquid crystal display element has an initial voltage holding ratio (voltage holding ratio, VHR) of 90% or more, or 90% to 100%, measured by using TOYO Corporation's 6254C equipment at a temperature of 1 Hz and 60 ° C. May be good.

Further, in the liquid crystal display element, the amount of change in the voltage holding ratio measured by the following formula 1 is 7% or less, 5% or less, 3% or less, or 0.1% to 7%, or 0.1%. It may be 5%, or 0.1% to 3%, or 1% to 3%, or 1.5% to 2.3%.
[Formula 1]
VHR rate of change (%) = initial VHR (V ₀ ) -after storage VHR (V ₁ )

In the above formula 1, the initial voltage retention rate (V ₀ ) is the voltage retention rate measured at 1 Hz and 60 ° C. temperature using TOYO Corporation's 6254C equipment as the measurement equipment for the liquid crystal oriented cell, and is VHR (V ₁ ) after storage. ) Is the voltage retention rate measured with the same equipment at 1 Hz and 60 ° C. temperature for the liquid crystal oriented cell stored under the same conditions for 120 hours.

Further, the luminance fluctuation rate of the liquid crystal display element may be less than 10%. The luminance fluctuation rate is such that a polarizing plate is attached to the upper plate and the lower plate of the liquid crystal display element, and the liquid crystal display element to which the polarizing plate is attached is attached to a 7,000 cd / m ² backlight and is in a black state. The initial luminance (L0) measured by using the PR-880 equipment, which is the luminance brightness measurement equipment, and the luminance (L1) after the measurement after the liquid crystal display element was driven at room temperature at an AC voltage of 5 V for 24 hours. It can be obtained by dividing the difference between them by the initial brightness (L0) value and multiplying by 100. When the luminance fluctuation rate of the liquid crystal display element increases to 10% or more, it can be evaluated that the afterimage characteristic of the liquid crystal display element is poor.

According to the present invention, since the discoloration property is low even during long-term storage, an excellent light transmittance can be exhibited when applied to a liquid crystal alignment film, and a liquid crystal alignment agent composition capable of realizing improved orientation and electrical characteristics. , A method for producing a liquid crystal alignment film using this, and a liquid crystal alignment film and a liquid crystal display element using the same can be provided.

The invention will be described in more detail with reference to the following examples. However, the following examples are merely examples of the present invention, and the content of the present invention is not limited to the following examples.

<Manufacturing example: Manufacture of diamine>

１８．３ｇ（１００ｍｍｏｌ）の２－クロロ－５－ニトロピリジン（２－ｃｈｌｏｒｏ－５－ｎｉｔｒｏｐｙｒｉｄｉｎｅ、化合物１）、１２．５ｇ（９８．６ｍｍｏｌ）のパラフェニレンジアミン（ｐ－ＰＤＡ、化合物２）を２００ｍＬのジメチルスルホキシド（Ｄｉｍｅｔｈｙｌｓｕｌｆｏｘｉｄｅ、ＤＭＳＯ）に完全に溶かした後、２３．４ｇ（２００ｍｍｏｌ）のトリエチルアミン（ｔｒｉｅｔｈｙｌａｍｉｎｅ、ＴＥＡ）を添加し、常温で１２時間攪拌した。反応が終結すると反応物を５００ｍＬの水が入っている容器に投入し、１時間攪拌した。これを濾過して得た固体を２００ｍＬの水と２００ｍＬのエタノールで洗浄して１６ｇ（６１．３ｍｍｏｌ）の化合物３を合成した。（収率：６０％）

前記化合物３をエチルアセテート（ｅｔｈｙｌ ａｃｅｔａｔｅ、ＥＡ）とＴＨＦを１：１に混合した２００ｍＬ溶液に溶かした後、０．８ｇのパラジウム（Ｐｄ）／炭素（Ｃ）を投入して水素環境下で１２時間攪拌した。反応終了後、セライトパッドで濾過した濾液を濃縮して１１ｇの化合物４ジアミン（Ｎ－４－Ａｍｉｎｏｐｈｅｎｙｌ－２，５－ｐｙｒｉｄｉｎｅｄｉａｍｉｎｅ、ｐ－ＩＤＡ）を製造した。（収率：８９％） Production Example 1

200 mL of 18.3 g (100 mmol) 2-chloro-5-nitropyridine (2-chloro-5-nitropyridine, compound 1) and 12.5 g (98.6 mmol) para-phenylenediamine (p-PDA, compound 2) After being completely dissolved in dimethyl sulfoxide (DMSO), 23.4 g (200 mmol) of triethylamine (TEA) was added, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, the reaction product was put into a container containing 500 mL of water and stirred for 1 hour. The solid obtained by filtering this was washed with 200 mL of water and 200 mL of ethanol to synthesize 16 g (61.3 mmol) of compound 3. (Yield: 60%)

After dissolving the above compound 3 in a 200 mL solution in which ethyl acetate (EA) and THF are mixed 1: 1, 0.8 g of palladium (Pd) / carbon (C) is added and 12 in a hydrogen environment. Stir for hours. After completion of the reaction, the filtrate filtered through a cerite pad was concentrated to produce 11 g of compound 4diamine (N-4-Aminophenyl-2,5-pyridinediamine, p-IDA). (Yield: 89%)

前記パラフェニレンジアミン（ｐ－ＰＤＡ、化合物２）の代わりにメタフェニレンジアミン（ｍ－ＰＤＡ）を用いたことを除いては、前記製造例１と同様な方法で製造例２のジアミンを製造した。 Manufacturing example 2

The diamine of Production Example 2 was produced by the same method as in Production Example 1 except that meta-phenylenediamine (m-PDA) was used in place of the para-phenylenediamine (p-PDA, compound 2).

前記２－クロロ－５－ニトロピリジン（２－ｃｈｌｏｒｏ－５－ｎｉｔｒｏｐｙｒｉｄｉｎｅ、化合物１）の代わりに２－クロロ－４－ニトロピリジン（２－ｃｈｌｏｒｏ－４－ｎｉｔｒｏｐｙｒｉｄｉｎｅ）を用いたことを除いては、前記製造例１と同様な方法で製造例３のジアミンを製造した。 Production example 3

Except for the fact that 2-chloro-4-nitropyridine (2-chloro-4-nitropyridine) was used in place of the 2-chloro-5-nitropyridine (2-chloro-5-nitropyridine, compound 1). The diamine of Production Example 3 was produced by the same method as in Production Example 1.

<Example: Production of liquid crystal alignment agent composition and liquid crystal alignment film>

Example 1

(1) Production of Liquid Liquid Alignment Agent Composition After dissolving 7.60 g (38 mmol) of the diamine (N-4-Aminophenyl-2,5-pyridinidine) of Production Example 1 in NMP, 3,3', 4,4 11.77 g (40 mmol) of'-biphenyltetracarboxylic dianhydride (3,3', 4,4'-Biphenylethyltracarboxyl acid dianhydride) was stirred at 25 ° C. for 4 hours with an acid anhydride group attached to the end. A polymer for a liquid crystal aligning agent was synthesized. Subsequently, 0.44 g (4 mmol) of 1,3-aminophenol (1,3-Aminophenol) was added as a terminal modifier and stirred for 20 hours to prepare a liquid crystal alignment agent composition.

(2) Production of Liquid Crystal Alignment Film In (1) of Example 1 above, an ITO electrode having a thickness of 60 nm and an area of 1 cm x 1 cm is patterned and spun-coated on a square glass substrate having a size of 2.5 cm x 2.7 cm. The obtained liquid crystal alignment agent composition was applied. Next, the substrate coated with the liquid crystal alignment agent composition was placed on a hot plate at 80 ° C. and dried for 2 minutes. After that, using an exposure device with a linear polarizing element, ultraviolet rays of 254 nm were irradiated at an exposure amount of 0.25 J / cm ² for orientation treatment, and then baked (cured) in an oven at 230 ° C. for 15 minutes to obtain a thickness of 0. A 1 μm liquid crystal alignment film was produced.

Example 2
A liquid crystal alignment agent composition and a liquid crystal alignment film were produced in the same manner as in Example 1 except that aniline was added instead of 1,3-aminophenol as the terminal modifier.

<Comparative example: Production of liquid crystal alignment agent composition and liquid crystal alignment film>

Comparative Example 1
A liquid crystal alignment agent composition and a liquid crystal alignment film were produced in the same manner as in Example 1 except that the terminal modifiers 1,3-aminophenol were not added.

Comparative Example 2
As the terminal modifier, instead of 1,3-aminophenol, 5- (2,5-dioxotetrahydro-3-furanyl) -6-methylhexahydro-2-benzofuran-1, represented by the following chemical formula A, A liquid crystal alignment agent composition and a liquid crystal alignment film were produced in the same manner as in Example 1 except that 3-dione was used.
[Chemical formula A]

Comparative Example 3
Same as Example 1 except that p-phenylenediamine (p-PDA) was added instead of the diamine (N-4-Aminophenyl-2,5-pyridinediamine) of Production Example 1. The liquid crystal alignment agent composition and the liquid crystal alignment film were produced by the above methods.

<Experimental example: Measurement of physical properties of the liquid crystal alignment agent composition and the liquid crystal alignment film obtained in Examples and Comparative Examples>
Physical properties were measured by the following method from the liquid crystal alignment agent composition or the liquid crystal alignment film obtained in the above Examples and Comparative Examples, and the liquid crystal alignment cell manufactured by using the same, and the results are shown in Table 1. ..

The specific method for manufacturing a liquid crystal alignment cell is as follows. The liquid crystal alignment films formed on the two glass substrates used as the upper plate / lower plate are aligned with each other so that the orientation directions are aligned with each other, and then the upper and lower plates are joined together. Empty cells were manufactured by curing using a sealant. Then, the liquid crystal was injected into the empty cell, and the injection port was sealed with a sealing agent to manufacture a liquid crystal alignment cell.

1. 1. AC afterimage A polarizing plate was attached to the upper and lower plates of the liquid crystal alignment cell so as to be perpendicular to each other. The liquid crystal cell to which the polarizing plate was attached was attached to a backlight of 7,000 cd / m ² , and the brightness in the black state was measured using the PR-880 equipment, which is a luminance brightness measurement equipment. Then, the liquid crystal cell was driven at room temperature with an AC voltage of 5 V for 24 hours. After that, the brightness in the black state was measured in the same manner as described above with the voltage of the liquid crystal cell turned off. The brightness fluctuation rate was calculated by dividing the difference between the initial brightness (L0) measured before driving the liquid crystal cell and the post-luminance (L1) measured after driving by the initial brightness (L0) value and multiplying by 100. The closer the luminance volatility calculated in this way is to 0%, the better the orientation stability. The afterimage level was evaluated under the following criteria through the measurement results of the brightness change rate.
Excellent: Brightness fluctuation rate is less than 10% Normal: Brightness fluctuation rate is 10% to 20%
Defective: Brightness fluctuation rate exceeds 20%

2. 2. Long-term reliability of voltage holding ratio (VHR) For the liquid crystal alignment cell, the initial voltage holding ratio (V ₀ ) was measured at 1 Hz and 60 ° C. using TOYO corporation's 6254C equipment as the measurement equipment. .. Then, after storing for 120 hours under the same equipment and under the same conditions, the voltage holding rate (V ₁ ) is measured at a temperature of 1 Hz and 60 ° C., and the rate of change in the voltage holding rate is calculated by the following formula 1 to obtain long-term reliability. Was evaluated.
[Formula 1]
VHR rate of change (%) = initial VHR (V ₀ ) -after storage VHR (V ₁ )

3. 3. Long-term color change After storing the liquid crystal alignment agent compositions of Examples and Comparative Examples at room temperature (25 ° C.) and humidity within 40% for 120 hours, the method described in (2) of Example 1 is used. 1 A liquid crystal alignment film was manufactured.

Further, the liquid crystal alignment agent compositions of Examples and Comparative Examples were not stored for 120 hours at room temperature (25 ° C.) and humidity within 40%, but immediately by the method described in (2) of Example 1 above. A second liquid crystal alignment film was manufactured.

Hereinafter, the transmittance of each of the first liquid crystal alignment film and the second liquid crystal alignment film is measured at a wavelength of 400 nm using the JASCO Asia Portal V-770 UV-VIS-NIR Spectrophotometer equipment, and the transmittance is transmitted through the following formula 2. The rate of change was calculated and the long-term color change was evaluated.
[Formula 2]
Transmittance rate of change (%) = 2nd liquid crystal alignment film transmittance-1st liquid crystal alignment film transmittance

4. Storage stability For the liquid crystal alignment films of the above Examples and Comparative Examples, the initial viscosity and the viscosity after storage at room temperature (20 to 30 ° C.) for 30 days were measured, and the amount of change in viscosity was determined by the following formula 3. It was measured.

The viscosity of the liquid crystal alignment film can be measured by a temperature of 25 ° C., a rotation speed of 0.5 rpm, and a torque with a Brookfield viscometer on the RV-7 spindle.
[Formula 3]
Viscosity change amount (cps) = (Viscosity of liquid crystal alignment film after storage at room temperature for 30 days-viscosity of first liquid crystal alignment film)

As shown in Table 1, an amine compound such as 1,3-aminophenol or aniline was used as a terminal modifier together with a polyimide synthesized from p-IDA or a precursor polymer thereof in the liquid crystal alignment agent composition. The liquid crystal alignment agent composition of the example showed excellent orientation stability with the brightness fluctuation rate of the alignment cell obtained from this being less than 10%, and the change rate of VHR was 1.5% to 2.3 even during long-term storage. It is shown as low as% to show excellent electrical reliability, the rate of change in permeability of the alignment film is shown as low as 0.3% to 0.7% even during long-term storage, and the amount of change in viscosity is also shown as low as 2.01 cps to 2. Since it was as low as .41 cps, it was confirmed that the reliability of the alignment film was excellent.

On the other hand, the liquid crystal alignment agent composition of Comparative Example 1 containing no terminal modifier was shown to have a VHR change rate of 7.2% during long-term storage, which was much higher than that of Examples, and was stored for a long period of time. It was confirmed that the electrical reliability was poor, and the transmittance change rate of the alignment film increased to 3.4% during long-term storage, and the reliability of the alignment film also decreased.

In particular, in the liquid crystal alignment agent composition of Comparative Example 2 to which an additive having a dianhydride structure such as Chemical Formula A was applied, the rate of change of VHR was 13.4% during long-term storage, which was not only in Example but also in Comparative Example 1. It was shown to be very high compared to the above, and it was shown that the electrical reliability due to long-term storage was very poor, and the transmittance change rate of the alignment film increased to 1.0% during long-term storage as compared with the examples. However, it was confirmed that the amount of change in viscosity also increased sharply to 72 cps, and the reliability of the alignment film decreased.

On the other hand, in the case of Comparative Example 3 in which the diamine used for the synthesis of polyimide or its precursor polymer was changed to p-phenylenediamine widely used in the liquid crystal alignment agent field, the initial voltage retention rate (VHR) of 78% was shown. Not only does the initial voltage holding rate (VHR) of 99% decrease as compared to Example 1, but the rate of change of VHR rapidly increases to 15.8% during long-term storage, resulting in poor electrical characteristics. I was able to confirm. Moreover, it was confirmed that the luminance fluctuation rate increased to over 20% and the AC afterimage characteristics were poor.

Claims (13)

It contains one or more repeating units selected from the group consisting of the repeating unit represented by the following chemical formula 1, the repeating unit represented by the following chemical formula 2, and the repeating unit represented by the following chemical formula 3, and contains at least one terminal acid. Polymers to which an anhydride group is attached; and a terminal modifier compound containing an amino group,
Liquid crystal alignment agent composition:
[Chemical formula 1]

[Chemical formula 2]

[Chemical formula 3]

With the above chemical formulas 1 to 3,
At least one of R ₁ and R ₂ is an alkyl group with 1 to 10 carbon atoms and the rest is hydrogen.
X ₁ to X ₃ are independently tetravalent organic groups, respectively.
Y ₁ to Y ₃ are each independently a divalent organic group represented by the following chemical formula 4.
[Chemical formula 4]

With the above chemical formula 4,
A is nitrogen,
R ₃ is one of hydrogen, or an alkyl group having 1 to 10 carbon atoms.
a is 1
One of Z ₁ and Z ₃ is nitrogen, the rest is carbon,
Z ₂ and Z ₄ are carbon. In the chemical formula 4 , R ₃ is hydrogen .
The liquid crystal alignment agent composition according to claim 1. The chemical formula 4 contains one or more working groups selected from the group consisting of the following chemical formulas 4-1 and 4-2 and 4-3.
The liquid crystal alignment agent composition according to claim 1 or 2.
[Chemical formula 4-1]

[Chemical formula 4-2]

[Chemical formula 4-3]

Each of X1 to X3 independently contains _one of the tetravalent organic groups described in Chemical Formula ₅ below.
The liquid crystal alignment agent composition according to any one of claims 1 to 3.
[Chemical formula 5]

With the above chemical formula 5,
R ₄ to R ₉ are independently hydrogen or an alkyl group having 1 to 10 carbon atoms.
L ₁ is a direct bond, -O-, -CO-, -S-, -SO-, -SO _2- , -CR ₁₀ R _11- , -CONH-, -COO-,-(CH ₂ ) _b- , -O (CH ₂ ) _b O-, -COO- (CH ₂ ) _b -OCO-, phenylene, or any one selected from the group consisting of combinations thereof.
R ₁₀ and R ₁₁ are independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or a haloalkyl group having 1 to 10 carbon atoms, respectively.
b is an integer from 1 to 10. The terminal modifier compound containing an amino group is represented by the following chemical formula 6.
The liquid crystal alignment agent composition according to any one of claims 1 to 4.
[Chemical formula 6]

With the above chemical formula 6,
L ₂ and L ₃ are independently bonded, directly bonded, -O-, -CO-, -S-, -CONH-, -COO-, -O (CH ₂ ) _t O-, -COO- (CH). ₂ ) _t -OCO-, alkylene group having 1 to 10 carbon atoms, haloalkylene group having 1 to 10 carbon atoms, cycloalkylene group having 3 to 20 carbon atoms, heterocycloalkylene group having 3 to 20 carbon atoms, 6 carbon atoms. It is one of an arylene group of 30 to 30 or a heteroarylene group having 3 to 20 carbon atoms.
t is an integer from 1 to 10
X is one of hydrogen, a hydroxy group, a nitro group, or an alkyl group having 1 to 10 carbon atoms. The content of the terminal modifier compound containing an amino group is 0.1% by weight to 20% by weight based on the total weight of the liquid crystal alignment agent composition.
The liquid crystal alignment agent composition according to any one of claims 1 to 5. The polymer is
It contains one or more repeating units selected from the group consisting of the repeating unit represented by the chemical formula 1, the repeating unit represented by the chemical formula 2, and the repeating unit represented by the chemical formula 3, and contains an acid anhydride at least at one end. In addition to the polymer to which the group is bonded,
It contains one or more repeating units selected from the group consisting of the repeating unit represented by the chemical formula 1, the repeating unit represented by the chemical formula 2, and the repeating unit represented by the chemical formula 3, and at least one end thereof is the following chemical formula 7. , Further comprising a second polymer containing one or more end-acting groups selected from the group consisting of Chemical Formula 8 and Chemical Formula 9.
The liquid crystal alignment agent composition according to any one of claims 1 to 6.
[Chemical formula 7]

[Chemical formula 8]

[Chemical formula 9]

With the chemical formulas 7 to 9,
At least _one of R 1'and R _2'is an alkyl group with 1 to 10 carbon atoms and the rest is hydrogen.
X _1'to X _3'are independent tetravalent organic groups, respectively.
Y _1'to Y _3'are independent divalent organic groups represented by the following chemical formula 10 .
L _2'and L _3'are independent and directly bonded, -O-, -CO-, -S-, -CONH-, -COO-, -O (CH ₂ ) _t O-, -COO- (CH ₂ ) _t -OCO-, alkylene group having 1 to 10 carbon atoms, haloalkylene group having 1 to 10 carbon atoms, cycloalkylene group having 3 to 20 carbon atoms, heterocycloalkylene group having 3 to 20 carbon atoms, carbon. It is one of an arylene group having 6 to 30 carbon atoms or a heteroarylene group having 3 to 20 carbon atoms.
t is an integer from 1 to 10
X'is one of a hydrogen, a hydroxy group, a nitro group, or an alkyl group having 1 to 10 carbon atoms.
[Chemical formula 10 ]

With the above chemical formula 10 ,
A is nitrogen ,
R ₃ is one of hydrogen, or an alkyl group having 1 to 10 carbon atoms.
a is 1
At least one of Z ₁ to Z ₄ is nitrogen and the rest is carbon. The second polymer is contained in an amount of 0.5% by weight to 40% by weight based on the entire liquid crystal alignment agent composition.
The liquid crystal alignment agent composition according to claim 7. A step of applying the liquid crystal alignment agent composition according to any one of claims 1 to 8 to a substrate to form a coating film;
The stage of drying the coating film;
Includes a step of irradiating the dried coating film with light or rubbing it to perform an orientation treatment; and a step of heat-treating the oriented coating film to cure it.
A method for manufacturing a liquid crystal alignment film. The step of drying the coating film is carried out at a temperature of 50 ° C to 150 ° C.
The method for producing a liquid crystal alignment film according to claim 9. The step of heat-treating and curing the oriented coating film is carried out at a temperature of 180 ° C to 300 ° C.
The method for producing a liquid crystal alignment film according to claim 9 or 10. A cured product of the liquid crystal alignment agent composition according to any one of claims 1 to 8.
Liquid crystal alignment film. A liquid crystal display element including the liquid crystal alignment film according to claim 12.